External workload and cognitive performance of a tactical military scenario-based field exercise.

INTRODUCTION: Military personnel must manage a multitude of competing physiological and cognitive stressors while maintaining high levels of performance. Quantifying the external workload and cognitive demands of tactical military field exercises closely simulating operational environments, will provide a better understanding of stressors placed on personnel to inform evidence-based interventions. METHODS: Thirty-one soldiers completing a dismounted 48 hours tactical field exercise, participated in the study. External workload was quantified using a wrist-worn triaxial accelerometer, with cognitive function (Go-/No-Go, N-back, psychomotor vigilance task and subjective workload ratings (NASA-TLX) assessed pre-exercise, mid-exercise and postexercise. Physical activity was described using Euclidian Norm Minus One (mg), with moderate vigorous physical activity (MVPA) and sedentary light physical activity (SLPA) as ≥ or <113 mg, respectively. Changes in general cognitive performance (total accuracy-speed trade-off (ASTO) % change) and function outcome variables (overall mean reaction time, ASTO and number of correct and missed responses) were calculated for each assessment from pre-exercise, to mid-exercise and postexercise. RESULTS: For the exercise duration (50:12±02:06 hh:mm) participants spent more time completing SLPA compared with MVPA (1932±234 vs 1074±194 min; p<0.001), equating to 33% of the time spent completing MVPA. Overall cognitive performance decreased over the exercise (pre-to-post: -249). However, the largest decrement was observed pre-to-mid (-168). Perceived mental demand associated with the cognitive assessments significantly increased over the duration of the exercise (pre-: 33; mid-: 38 and post-: 51; χ2 F(2) = 26.7, p = <0.001, W=0.477) which could suggest that participants were able to attenuate a further decline in cognitive performance by investing more effort/mental resources when completing assessments. CONCLUSION: The study successfully quantified the physical activity, and subsequent impact on cognitive function, in soldiers completing a 48 hours tactical field exercise. Further research is needed to better understand how physiological stressors interact with cognitive function during military operations.

Structure and electron affinity of the 4H-SiC (0001) surfaces: a methodological approach for polar systems.

The ability to accurately and consistently determine the surface electronic properties of polar materials is of great importance for device applications. Polar surface modelling is fundamentally limited by the spontaneous polarisation of these materials in a periodic boundary condition scheme. Surface data are sensitive to supercell parameters, including slab and vacuum thicknesses, as well as the non-equivalence of surface adsorbates on opposite surfaces. Using 4H-SiC as a specific case, this study explores calculation of electron affinities (EAs) of (0001̄) and (0001) surfaces varying chemical termination as a function of computational parameters. We report the impact in terms of band-gap, electric fields across the vacuum and slab for single and double cell slab models, where the latter is constructed with inversional symmetry to eliminate the electric field in the vacuum regions. We find that single cells are sensitive to both slab and vacuum thickness. The band-gap narrows with slab thickness, ultimately vanishing and inducing charge transfer between opposite surfaces. This has a consequence for predicted EAs. Adsorbate species are found to play a crucial role in the rate of narrowing. Back to back cells with inversional symmetry have larger electric fields present across the slab than the single slab cases, resulting in a greater band-gap narrowing effect, but the vacuum thickness dependence is completely removed. We discuss the relative merits of the two approaches.

Silicon and germanium terminated (0 0 1)-(2 [Formula: see text] 1) diamond surface.

Control over the chemical termination of diamond surfaces has shown great promise in the realization of field-emission applications, the selection of charge states of near-surface colour-centres such as NV, and the realisation of surface-conductive channels for electronic device applications. Experimental investigations of ultra-thin Si and Ge layers yield surface states both within the band-gap and resonant with the underlying diamond valence band. In this report, we report the results of density-functional simulations of a range of coverages of Si and Ge on diamond (0 0 1) surfaces. We have found that surface coverage with crystallogen:carbon ratios of 67% and 75% are more stable than both higher and lower coverages on the (0 0 1)-diamond surface, and that they can explain the observation of an occupied band around 1.7 eV below the valence band top. We also report geometries, adsorption energies and electron affinities of these surface structures, and show that the resonant state is made up from conventional spd-covalent [Formula: see text]-bonding orbitals between the surface adsorbates.

Interlayer vacancy defects in AA-stacked bilayer graphene: density functional theory predictions.

AA-stacked graphite and closely related structures, where carbon atoms are located in registry in adjacent graphene layers, are a feature of graphitic systems including twisted and folded bilayer graphene, and turbostratic graphite. We present the results of ab initio density functional theory calculations performed to investigate the complexes that are formed from the binding of vacancy defects across neighbouring layers in AA-stacked bilayers. As with AB stacking, the carbon atoms surrounding lattice vacancies can form interlayer structures with sp 2 bonding that are lower in energy than in-plane reconstructions. The sp 2 interlayer bonding of adjacent multivacancy defects in registry creates a type of stable sp 2 bonded 'wormhole' or tunnel defect between the layers. We also identify a new class of 'mezzanine' structure characterised by sp 3 interlayer bonding, resembling a prismatic vacancy loop. The V 6 hexavacancy variant, where six sp 3 carbon atoms sit midway between two carbon layers and bond to both, is substantially more stable than any other vacancy aggregate in AA-stacked layers. Our focus is on vacancy generation and aggregation in the absence of extreme temperatures or intense beams.

Cyclotetrahalo-p-phenylenes: simulations of halogen substituted cycloparaphenylenes and their interaction with C60.

Density functional calculations are used to study the role of edge-functionalization on the structure and electronic properties of cycloparaphenylene (CPPs) containing from six to twenty benzenoid rings. We substitute hydrogen by the halogens fluorine, chlorine and bromine. The resultant Cyclotetrahalo-p-phenylenes are compared with their hydrogenated equivalents, related linear paraphenyl and fluoro-paraphenyl polymers, and functionalised armchair edges in graphene nanoribbons. Notably we consider both structural and electronic evolution. Finally we examine C60@[10]CPP, i.e. C60 encapsulated within [10]CPP, with the various ring terminations. The effect of halogenation on electronic level position around the gap strongly affects their capacity to form donor-acceptor pairs with fullerenes.

Surface-state dependent optical properties of OH-, F-, and H-terminated 4H-SiC quantum dots.

Density functional calculations are performed for OH-, F- and H-terminated 4H-SiC 10-20 Å diameter clusters to investigate the effect of surface species upon the optical absorption properties. H-termination results in a pronounced size-dependent quantum-confinement in the absorption, whereas F- and OH-terminations exhibit much reduced size dependent absorption due to surface states. Our findings are in good agreement with recent experimental studies, and are able to explain the little explored dual-feature photoluminescence spectra of SiC quantum dots. We propose that along with controlling the size, suitable surface termination is the key for optimizing optical properties of 4H-SiC quantum structures, such as might be exploited in optoelectronics, photovoltaics and biological applications.

Physical employment standards for U.K. fire and rescue service personnel.

BACKGROUND: Evidence-based physical employment standards are vital for recruiting, training and maintaining the operational effectiveness of personnel in physically demanding occupations. AIMS: (i) Develop criterion tests for in-service physical assessment, which simulate the role-related physical demands of UK fire and rescue service (UK FRS) personnel. (ii) Develop practical physical selection tests for FRS applicants. (iii) Evaluate the validity of the selection tests to predict criterion test performance. METHODS: Stage 1: we conducted a physical demands analysis involving seven workshops and an expert panel to document the key physical tasks required of UK FRS personnel and to develop 'criterion' and 'selection' tests. Stage 2: we measured the performance of 137 trainee and 50 trained UK FRS personnel on selection, criterion and 'field' measures of aerobic power, strength and body size. Statistical models were developed to predict criterion test performance. Stage 3: matter experts derived minimum performance standards. RESULTS: We developed single person simulations of the key physical tasks required of UK FRS personnel as criterion and selection tests (rural fire, domestic fire, ladder lift, ladder extension, ladder climb, pump assembly, enclosed space search). Selection tests were marginally stronger predictors of criterion test performance (r = 0.88-0.94, 95% Limits of Agreement [LoA] 7.6-14.0%) than field test scores (r = 0.84-0.94, 95% LoA 8.0-19.8%) and offered greater face and content validity and more practical implementation. CONCLUSIONS: This study outlines the development of role-related, gender-free physical employment tests for the UK FRS, which conform to equal opportunities law.

On the validity of empirical potentials for simulating radiation damage in graphite: a benchmark.

In this work, the ability of methods based on empirical potentials to simulate the effects of radiation damage in graphite is examined by comparing results for point defects, found using ab initio calculations based on density functional theory (DFT), with those given by two state of the art potentials: the Environment-Dependent Interatomic Potential (EDIP) and the Adaptive Intermolecular Reactive Empirical Bond Order potential (AIREBO). Formation energies for the interstitial, the vacancy and the Stone-Wales (5775) defect are all reasonably close to DFT values. Both EDIP and AIREBO can thus be suitable for the prompt defects in a cascade, for example. Both potentials suffer from arefacts. One is the pinch defect, where two α-atoms adopt a fourfold-coordinated sp(3) configuration, that forms a cross-link between neighbouring graphene sheets. Another, for AIREBO only, is that its ground state vacancy structure is close to the transition state found by DFT for migration. The EDIP fails to reproduce the ground state self-interstitial structure given by DFT, but has nearly the same formation energy. Also, for both potentials, the energy barriers that control diffusion and the evolution of a damage cascade, are not well reproduced. In particular the EDIP gives a barrier to removal of the Stone-Wales defect as 0.9 eV against DFT's 4.5 eV. The suite of defect structures used is provided as supplementary information as a benchmark set for future potentials.

Nitrogen segregation in nanocarbons.

We explore the behaviour of nitrogen doping in carbon nanomaterials, notably graphene, nanotubes, and carbon thin films. This is initially via a brief review of the literature, followed by a series of atomistic density functional calculations. We show that at low concentrations, substitutional nitrogen doping in the sp(2)-C graphenic basal plane is favoured, however once the nitrogen concentration reaches a critical threshold there is a transition towards the formation of the more thermodynamically-favoured nitrogen terminated 'zigzag' type edges. These can occur either via formation of finite patches (polycyclic aromatic azacarbons), strips of sp(2) carbon with zigzag nitrogen edges, or internal nitrogen-terminated hole edges within graphenic planes. This transition to edge formation is especially favoured when the nitrogen can be partially functionalised with, e.g. hydrogen. By comparison with available literature results, notably from electron energy loss spectroscopy and X-ray spectroscopy, the current results suggest that much of the nitrogen believed to be incorporated into carbon nanoobjects is instead likely to be present terminating the edges of carbonaceous impurities attached to nanoobject's surface. By comparison to nitrogen-doped tetrahedrally amorphous carbon, we suggest that this transition at around 10-20% nitrogen concentration and above towards sp(2) coordination via internal nitrogen-terminated edge formation may be a general property of nitrogen-doped carbon materials.

Identification of the structure of the 3107 cm(-1) H-related defect in diamond.

A prominent hydrogen-related infrared absorption peak seen in many types of diamonds at 3107 cm(-1) has been the subject of investigation for many years. It is present in natural type-Ia material and can be introduced by heat-treating synthetic or CVD diamond. Based upon the most recent experimental data, it is thought that the defect giving rise to this vibrational mode is vacancy-related and is likely to contain nitrogen. Using first-principles simulations we present a VN3H model for the originating centre that simultaneously satisfies the different experimental observations including the strain response.

Validity of 24-h recalls in (pre-)school aged children: comparison of proxy-reported energy intakes with measured energy expenditure.

BACKGROUND & AIMS: Little is known about the validity of repeated 24-h dietary recalls (24-HDR) as a measure of total energy intake (EI) in young children. This study aimed to evaluate the validity of proxy-reported EI by comparison with total energy expenditure (TEE) measured by the doubly labeled water (DLW) technique. METHODS: The agreement between EI and TEE was investigated in 36 (47.2% boys) children aged 4-10 years from Belgium and Spain using subgroup analyses and Bland-Altman plots. Low-energy-reporters (LER), adequate-energy-reporters (AER) and high-energy-reporters (HER) were defined from the ratio of EI over TEE by application of age- and sex-specific cut-off values. RESULTS: There was good agreement between means of EI (1500 kcal/day) and TEE (1523 kcal/day) at group level though in single children, i.e. at the individual level, large differences were observed. Almost perfect agreement between EI and TEE was observed in thin/normal weight children (EI: 1511 kcal/day; TEE: 1513 kcal/day). Even in overweight/obese children the mean difference between EI and TEE was only -86 kcal/day. Among the participants, 28 (78%) were classified as AER, five (14%) as HER and three (8%) as LER. CONCLUSION: Two proxy-reported 24-HDRs were found to be a valid instrument to assess EI on group level but not on the individual level.

Insulated skin temperature as a measure of core body temperature for individuals wearing CBRN protective clothing.

This study assessed the validity of insulated skin temperature (Tis) to predict rectal temperature (Tre) for use as a non-invasive measurement of thermal strain to reduce the risk of heat illness for emergency service personnel. Volunteers from the Police, Fire and Rescue, and Ambulance Services performed role-related tasks in hot (30 °C) and neutral (18 °C) conditions, wearing service specific personal protective equipment. Insulated skin temperature and micro climate temperature (Tmc) predicted Tre with an adjusted r(2) = 0.87 and standard error of the estimate (SEE) of 0.19 °C. A bootstrap validation of the equation resulted in an adjusted r(2) = 0.85 and SEE = 0.20 °C. Taking into account the 0.20 °C error, the prediction of Tre resulted in a sensitivity and specificity of 100% and 91%, respectively. Insulated skin temperature and Tmc can be used in a model to predict Tre in emergency service personnel wearing CBRN protective clothing with an SEE of 0.2 °C. However, the model is only valid for Tis over 36.5 °C, above which thermal stability is reached between the core and the skin.

Extended interplanar linking in graphite formed from vacancy aggregates.

The mechanical and electrical properties of graphite and related materials such as multilayer graphene depend strongly on the presence of defects in the lattice structure, particularly those which create links between adjacent planes. We present findings which suggest the existence of a new type of defect in the graphite or graphene structure which connects adjacent planes through continuous hexagonal sp2 bonding alone and can form through the aggregation of individual vacancy defects. The energetics and kinetics of the formation of this type of defect are investigated with atomistic density functional theory calculations. The resultant structures are then employed to simulate high resolution transmission electron microscopy images, which are compared to recent experimental images of electron irradiation damaged graphite.

Hyperfine interactions at nitrogen interstitial defects in diamond.

Diamond has many extreme physical properties and it can be used in a wide range of applications. In particular it is a highly effective particle detection material, where radiation damage is an important consideration. The WAR9 and WAR10 are electron paramagnetic resonance centres seen in irradiated, nitrogen-containing diamond. These S = 1/2 defects have C(2v) and C(1h) symmetry, respectively, and the experimental spectra have been interpreted as arising from nitrogen split-interstitial centres. Based upon the experimental and theoretical understanding of interstitial nitrogen defect structures, the AIMPRO density functional code has been used to assess the assignments for the structures of WAR9 and WAR10. Although the calculated hyperfine interaction tensors are consistent with the measured values for WAR9, the thermal stability renders the assignment problematic. The model for the WAR10 centre yields principal directions of the hyperfine tensor at variance with observation. Alternative models for both centres are discussed in this paper, but no convincing structures have been found.

The IDEFICS validation study on field methods for assessing physical activity and body composition in children: design and data collection.

OBJECTIVE: To describe the design, measurements and fieldwork of the IDEFICS (Identification and prevention of dietary- and lifestyle-induced health effects in children and infants) physical activity and body composition validation study, and to determine the potential and limitations of the data obtained. DESIGN: Multicentre validation study. SUBJECTS: A total of 98 children from four different European countries (age: 4-10 years). METHODS: An 8-day measurement protocol was carried out in all children using a collaborative protocol. Reference methods were the doubly labelled water method for physical activity, and a three- and a four-compartment model for body composition. Investigated field methods were accelerometers, a physical activity questionnaire and various anthropometric measurements. RESULTS: For the validation of physical activity field methods, it was possible to gather data from 83 to 89 children, laying the basis for age- and sex-specific results. The validation of body composition field methods is possible in 64-80 children and allows sex-specific analyses but has only limited statistical power in the youngest age group (<6 years). The amount of activity energy expenditure (AEE) varied between centres, sexes and age groups, with boys and older children having higher estimates of AEE. After normalisation of AEE by body weight, most group-specific differences diminished, except for country-specific differences. CONCLUSION: The IDEFICS validation study will allow age- and sex-specific investigation of questions pertaining to the validity of several field methods of body composition and physical activity, using established reference methods in four different European countries. From the participant analyses it can be concluded that the compliance for the investigated field methods was higher than that for the reference methods used in this validation study.

Reliability and validity of the 3DNX accelerometer during mechanical and human treadmill exercise testing.

OBJECTIVE: This study aimed to assess the validity and reliability of the 3DNX triaxial accelerometer in a laboratory and mechanical setting. METHODS: Experiment 1: A total of 10 units were fixed to a Multi-axis shaker table. A schedule comprising a range of accelerations was repeated on two occasions along each of the three measurement axes. Experiment 2: A total of 11 recreationally active individuals completed a treadmill protocol (4-20 km hr(-1)) on two occasions. Two 3DNX accelerometers were secured to the lower back, logging data every 5 s. Oxygen uptake was measured using the Douglas Bag technique. Reliability inter- and intra-units were assessed using a combination of limits of agreement (LoA), coefficient of variation (CV) and intra-class correlation coefficient (ICC). Validity was assessed using simple linear regression. All data are expressed in counts per 5 s (counts 5 s(-1)). RESULTS: Experiment 1: CV(intra) ranged from 0.0 to 8.9% in all axes. The absolute bias±95% LoA values were all below four counts 5 s(-1). CV(inter) did not rise above 4.5%. ICCs were 1.0 for all stages in all axes. The relationship between 3DNX counts and acceleration yielded an R(2) value of 0.99 and a standard error of the estimate (SEE) of six counts 5 s(-1). Experiment 2: CV(inter) ranged from 7.7 to 16.0% for trial 1 and from 7.7 to 16.2% for trial 2. ICCs between units ranged from 0.95 to 1.00 for trial 1 and from 0.90 to 0.99 for trial 2. Mean ratio bias±95% LoA values for intra-unit and inter-unit reliability were -0.7% (P>0.05)±12.4% and 0.4% (P>0.05)±5.6%, respectively. The relationship between VO(2) and 3DNX counts for walking and running was linear (R(2)=0.65, SEE=1.42 ml kg(-1) min(-1); R(2)=0.62, SEE=3.63 ml kg(-1) min(-1)). CONCLUSION: The 3DNX accelerometer is a reliable and valid device for measuring acceleration in a mechanical setting and during human treadmill exercise.

Physical demands of firefighter search and rescue in ambient environmental conditions.

This study investigated the physiological responses and limitations to a simulated search and rescue scenario in a high-rise building under ambient conditions. Sixteen firefighters performed the scenario under four conditions: standard duration breathing apparatus (SDBA) and 45 mm hose; extended duration breathing apparatus (EDBA) and 45 mm hose; SDBA and 70 mm hose; EDBA and 70 mm hose. Core temperature, skin temperature and heart rate were monitored. In four of 32 trials the casualty was rescued; the remainder of the trials were terminated for safety, high core temperature or shortage of air. Final core temperature and heart rate were higher in the EDBA (39.1 degrees C; 72% heart rate reserve (HRR)) than SDBA conditions (38.6 degrees C; 67%HRR). No differences were observed between hose sizes. The scenario proved too onerous to complete successfully in the majority of cases. Replacing SDBA with EDBA eliminates air supply as a limiting factor, but brings with it challenges of managing thermal strain.

Lagrange-Lobatto interpolating polynomials in the discrete variable representation.

The discrete variable representation (DVR) is a well known and widely used computational technique in many areas of physics. Recently, the Lagrange-Lobatto basis has attracted increasing attention, especially for radial Hamiltonians with a singular potential at the origin and finite element DVR constructions. However, unlike standard DVR functions, the Lagrange-Lobatto basis functions are not orthogonal. The overlap matrix is usually approximated as the identity using the same quadrature approximation as for the potential. Based on the special properties of overlap matrix of Lagrange-Lobatto polynomials, an explanation of the success of the identity approximation, including error bounds, is presented. Results for hydrogen and the more nontrivial potentials of self-consistent all-electron density functional atomic calculations are also given.

Can simple anthropometric and physical performance tests track training-induced changes in maximal box-lifting ability?

The objective of this research was to determine if tests of lifting strength and anthropometry could be used to assess training-induced changes in box-lift performance. Ninety-two British Army recruits completed a 10-week training programme. Isometric and dynamic lifting strength, body composition and maximal box-lift to 1.45 m and 1.70 m were assessed before and after training. Training significantly increased box-lift performance, dynamic lifting strength and fat-free mass, and reduced body fat. Statistically significant regression models (adjusted R(2) of 0.299 and 0.152) were produced that predicted the changes in box-lift performance from changes in body composition and lifting strength. However, the 95% limits of agreement between the observed and predicted change in box-lift performance showed wide margins of error (11-13 kg; 26-29%). Training-induced changes in box-lift performance appear to be highly specific, which suggests that both training and testing procedures should also be specific to box-lift performance.

Importance of quantum tunneling in vacancy-hydrogen complexes in diamond.

Our ab initio calculations of the hyperfine parameters for negatively charged vacancy-hydrogen and nitrogen-vacancy-hydrogen complexes in diamond compare static defect models and models which account for the quantum tunneling behavior of hydrogen. The static models give rise to hyperfine splittings that are inconsistent with the experimental electron paramagnetic resonance data. In contrast, the hyperfine parameters for the quantum dynamical models are in agreement with the experimental observations. We show that the quantum motion of the proton is crucial to the prediction of symmetry and hyperfine constants for two simple defect centers in diamond. Static a priori methods fail for these systems.